Photographic color picture



Patented Jan. 9, 1940 UNITED STATES PATENT ,OFFISE rno'rocnarmc coma rrc'rmm No Drawing. Application April 3, 1939, Serial No. 265,759. In Germany April 9, 1938 8 Claims.

Our present invention relates to the manufacture of photographic color pictures.

In a process for producing color photographic pictures with aid of color development there, are used as dyestufi formers compounds which during the development with a developer containing a free amino-group, for instance para-phenylenediamine or para-aminophenol, yield a dyestufl' image on the silver image. For obtaining blue 10- dyestufls there have hitherto been used by preference phenols and naphthols and derivatives thereof. These dyestufl formers yield during development blue to blue-green quinoneimine dyeapplication describes components which contain Our present invention has for one object to provide a process of making blue-violet and redviolet photographic pictures.

Another object of our invention is to provide a process of producing such pictures wherein 20 there are used as dyestufi formers compounds of the general formula V or substituted phenylene.

A further object of this invention is the provision of a dyestufi forming developer which contains such dyestufi former.

35 more in detail hereinafter.

Compounds of this kind are, for example, 2- methyl-indole, 2.5-dimethylindole, 4-phenyl-2- methyl-pyrrolei-carboxylic acid ethyl ester, 2- methyl-pyrrole-3-carboxylic acid ethyl ester, '2- methyl-pyrrole. v

These dyestufl? components may be added to the developer or to the emulsion. When the component is added to the developing solution it is recommended that it should first be dissolved in an organic solvent,-forinstance alcohol or acetone, and this solution should be added to the developer.

when the dyestuff former is to be added to the photographicsilver halide emulsion those tonners are'gespecially suitable which, owing to the introduction of special groups, are fast to diffusion with respect to the binding agent 0! the emulsion. This expedient is especially of importance in the case oi dyestufl! formers which such as an aminoor hydroxy group.

Other objects of our invention will appear ber 29, 1937, 175,285'fi1ed November 18, 1937, 19

176,058 filed November 23, 1937, 191,952 filed February 23, 1938, and in the British patent specification No. 488,048. Said last named U. S.

in addition to a group rendering the component 7 fast to diffusion a solubilizing group such as a carboxy group. The components are prepared by reacting the internal anhydride of a poly- ;basic organic acid, such as the anhydrides of maleic acid, succinic acid, pyrotartaric acid and 20 the like containing for example a long aliphatic chain, i. e. of at least 5 carbon atoms such as octadecylene, isodecylene, iso-nonylene' and the like with a color former containing a reactive group The ring of the anhydride is thereby split in such a manner that one CO-group unites with the reactive group and the other forms a carboxy group. As

the color former there may be used p-amino-aceto-acetic anilide, 4-amino-1-phenyl-3-methyl-5- pyrazolone, l-amino-5-naphthol and the like. As the anhydride'there may be used octadecylene succinic acid anhydride a-dodecylea-hexahydrobenzene-pyro-tartaric. acid anhydride and the like. It has been explained in the said applica- 3 tions that the radicles which impart fastness-to difiusion may be introduced in a manner in itself known, for example by way of amino-, hydroxy- 0r carboxyl-groups, with the formation of an acid amide or an ester. For example, it is possible 40 to cause 2-methyl-pyrrole-3-carboxylic acid ethyl ester to react with undecylamine. It is also possible to unite the radlcle which imparts fastness to diffusion directly tothe nitrogen atom without interposition of an acid group or direct- 1y to the benzene nucleus. Silver halide emulsion layers comprising such dyestufi components may be applied singly or together with other layers on one or both sides of a carrier to produce a multi-layer material in which the layers are sensitized for difierent regions of the spectrum.

' It is also possible to distribute the particles of emulsion containing various dyestufi formers on a carrier. With the aid of this latter material screen pictures may be produced.

The silver halide emulsion layers containing the dyestuff formers may be united with other layers generally used in the production of photographic materials, for example filter layers, antihalation layers, matting layers, backing layers. They may also be combined with photographic layers in which color pictures are to be produced by any other process for instance by the silver bleaching out dyestufi process or the toning process. As binding agent for the photographic emulsions gelatin or any other colloid usual in photographic practice may be used.

The following examples illustrate the invention:

Example 1.An exposedsilver halide emulsion layer is developed with a developer of the following composition: 1.6 grams 2-methyl-pyrro1e-3- carboxylic acid ethyl ester of the formula HCC.CO 0 Calls Methanol cc 60 Para-diethylaminoaniline hydrochloride grams 2 Crystalliz'ed sodium carbonate do Anhydrous sodium sulfite do 2 Potassium bromide do 0.2

Water cc 1000 After the silver has been dissolved there remains a blue-violet dyestufi image.

Example 2.--An exposed silver halide emulsion layer is developed with a developer of the following composition: 2.3 grams 2-methyl-4-phenylpyrrole-S-carboxylic acid ethyl ester of the for mula H5Cq.(fiC-COOCZHB \HC c.o11=

Methanol cc Para-diethylaminoaniline hydrochloride "grams-.. 2 Crystallized sodium carbonate do 50 Anhydrous sodium sulfite do 2 Potassium bromide do 02 Water cc 1000 After dissolving the silver there remains a blueviolet dyestufi image. 1

Example 3.-An exposed silver halide emulsion layer is developed with a developer of the following composition:

2-methylindole gramsn Methanol cc Para-diethylaminoaniline hydrochloride I "grams" 2 crystallized sodium carbonate do 50 Anhydrous sodium sulfite do 2 Potassium bromide do 0.2 Water cc 600 methanol (about 20 cc.) and added to 100 cc. of

a solution of the followingcomposition: Diethylphenylenediamine hydrochloride The exposed film is developed for eight minutes in this solution which, if necessary, has been clarified by adding methanol and filtered. After fixing and bleaching by means of potassium ferricyanide a violettish picture is obtained.

Example 6.-0.5 gram of 2.5-dimethylindole is dissolved in methanol and added to 100 cc. of a solution having the composition described in Example 5; The film is developed and worked-up in the same manner as mentioned in Example 5. A red-violet picture is obtained.

Example 7. 0.5 gram of 2-methyl-4-phenyl- 3-acetylpyrrole is dissolved in methanol and added to 100 cc. of a solution having the composition described in Example 5." The film is developed and worked up in the same manner as mentioned in Example 5.' A blue picture is obtained.

Example 8. 0.5 gram of 2-methyl-4-phenyl- 3-cinnamoylpyrrole is dissolved in methanol and added to 100 cc. of a solution having the composition described in Example 5. The film is developed and worked up in the same manner as mentioned in Example 5. A blue-violet picture is obtained.

Example 9.-0.5 gram of 2-methyl-4-phenylpyrrole-3-carboxylic acid is dissolved in methanol and added to 100 cc. of a solution having the composition described in Example 5. The film is developed and worked up .in the same manner as mentioned in Example 5. A blue-violet picture is obtained.

Example 10. 0.5 gram of 2.4-dimethyl-3-acetylpyrrole is dissolved in methanol and added to cc; of a solution having the composition described in Example 5. The film is developed and worked up in the same manner as mentioned in Example 5. A blue-violet picture is obtained.

Example 11. 0.5 gram of 2-me'thyl-4-phenyl- 3-benzoylpyrrole is dissolved in methanol and added to 100 cc. of a solution having the composition described in Example 5. The film is developed and worked up in the same manner as mentioned in Example 5. A blue-violet picture is obtained.

Example 12.3 grams of the condensation product from 2' mols of 2-mcthyl-4-phenyl3- acetylpyrrole and 1 mol of diphenyl-dialdehyde is dissolved in 60 cc. of acetone. The solution is added to 1 kilo of a silver halide gelatin emulsion. The emulsion is then cast to form a layer of a photographic multi-layer material. A-blue-violet picture is.obtained in this layer.

Example 13.-2 methyl-4 phenyl-3-acetylpyremulsion may be used for the manufacture of a multi layer material. A blue-violet picture is obtained in this emulsion layer.

Weclaim: v

1. In a process of producing photographic the step which comprises causing as the dyestufl wherein R is a member selected from the class consisting of hydrogen, alkyl, aryl, aralkyl, carboxyl, esterified carboxyl, and aminated carboxyl and x is a member selected from the class consisting of vinylene, substituted vinylene, phenylene, and substituted phenylene, to react with the oxidation product of an aromatic developer.

2. In a process of producing photographic color pictures by dyestufi forming development, the step which comprises developing the exposed photographic silver halide emulsion with an aromatic amino developer containing as the dyestufi former a compound of the general formula x o-om f Y wherein" I R is a member selected from the class consist ing of hydrogen, alkyl, aryl, aralkyl, carboxyl, esterified ca'rbcxyl, and aminated carboxyl and x is a member selected from the class consisting of vinylene, substituted vinylene, phenylene, and substituted phenylene.

3 In a process of producing photographic color pictures by dyestufl forming development, the step which comprises exposing a photographic silver halide emulsion containing as the dyestufl iormer a compound of the general formula wherein R is a member selected from the class consisting of hydrogen, alkyl, aryl, aralkyl, carboxyl, esterified carboxyl, and aminated car- C boxyl and Q X is a member selected from the class consist- .ing of vinylene, substituted vinylene, phenylene, and substituted phenylene,

said compound containing a radicle imparting thereto i'astness to diffusion with respect to the w wherein binding agent of said emulsion, and developing said emulsion with an aromatic amino developer.

4. Silver halide emulsion for color photography comprising a compound 01 the generaliormula R is a member selected from the class consisting of hydrogen, alkyl, aryl, aralkyl, carboxyl, esterified carboxyl, and aminated carboxyl and X is a member selected from the class consisting of vinylene, substituted vinylene, phenyl ene, and substituted phenylene, said compound containing a radicle imparting thereto fastness to difiusion with respect to the binding agent of said emulsion.

5. A dyestufi forming developer comprising an aqueous solution containing an aromatic amino developing agent and a compound of the general formula R is a member selected from the class consist- .ing of hydrogen, alkyl, aryl, aralkyl, carboxyl, esterified carboxyl, and aminated car- I boxylic acid ethyl ester with undecylamine;

8. A silver halide emulsion ior color photography containing as the color forming component a 2-methyl-indole substituted in 5-position by a member of the group consisting of methyl and hydrogen, said indole having attached thereto a. radicle which renders the indole fast to difiusion with respect to the binding agent of the emulsion.

W'ILHEIM SCHNEDER. HANS LOLEIT. 

